arXiv subjects

Joan Enrique-Romero

Publications and source records attributed to Joan Enrique-Romero.

17 recordsLinked to original sources

arXiv2026

Interstellar disparity: N- vs O-bearing molecules: A multidisciplinary perspective across interstellar environments

Observations of O- and N-bearing molecules reveal systematic chemical differentiation across a wide range of interstellar environments. This pattern is peculiar and its origin likely reflects a combination of physical conditions, chemical pathways, and observational effects rather than a single mechanism. In this paper, we provide a comprehensive overview of the current understanding of the N-bearing and O-bearing species and their relative behaviour in the interstellar medium, integrating results from observations, laboratory experiments, chemical modelling, and theoretical studies. While inspired by discussions at the Lorentz Center workshop held in Leiden in August 2025, this work goes beyond a summary of the meeting and instead synthesizes the state of the field, highlights key open questions, and outlines future directions. We identify several key observational, experimental, and theoretical challenges that must be addressed to determine the origin of this chemical differentiation.

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arXiv2026

Methanimine as a sink in the HCN and HNC solid state hydrogenation network

We aim to provide a systematic and quantitative description of the hydrogenation network connecting HCN and HNC to methylamine on interstellar water ices, while identifying dominant pathways and bottlenecks. To this end, we performed a comprehensive quantum-chemical investigation of H-addition, H-abstraction, reactions with H2, and water-assisted H-transfer isomerization, covering intermediates linking HCN and HNC to CH3NH2. Calculations were carried out on amorphous solid water clusters of 14 molecules. Using benchmarked density functional theory, we derived activation barriers, elucidated mechanisms, and determined the binding energy distribution of H2CN and CNH2, also assessing deuterium substitution effects. H-addition reactions generally involve activation barriers, except for radical species. Considering both barrier heights and tunneling crossover temperatures, the most favorable sequence originates from HNC rather than HCN. The network evolves toward methanimine (H2CNH), the central species, or the singlet carbene HC:NH2, from which further hydrogenation leads to methylamine. Along these paths, several reactions are barrierless, while some H-abstraction processes compete with addition. Reactions involving H2 are uncommon, as most are endoergic. Deuterium substitution weakly affects classical barriers but significantly influences tunneling efficiencies. Our results support efficient formation of methanimine and methylamine from HNC on cold interstellar ices, with methanimine acting as a chemical sink, whereas HCN is less reactive and more likely to persist. These findings provide quantitative constraints for astrochemical models.

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arXiv2026

Can cyanide radicals drive molecular backbone growth on interstellar icy grains?

Motivated by the value of CN-bearing molecules as tracers of interstellar physical conditions, we investigate the reactions of adsorbed CN radicals with acetylene and ethylene (C2H2 and C2H4) on interstellar dust-grain analogues using quantum chemical calculations. We find that reactivity is strongly controlled by the relative orientation of the reactants, with specific geometries either promoting or inhibiting reaction. We further show that, on ice, these reactions differ qualitatively from their gas-phase counterparts, stalling at the formation of the adduct complexes C2H2CN and C2H4CN and exhibiting newly emerged kinetic barriers for the neutral-radical association. We contextualize our calculations in the same reaction-diffusion framework that would be employed in astrochemical models, finding that, depending on the diffusion energy of the hydrocarbons, these reactions can be either negligible or efficient, highlighting the importance of the local ice structure in interstellar grain chemistry. These findings caution against the use of CN-based tracers that assume barrierless, bimolecular surface reactions involving CN radicals.

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arXiv2025

Interstellar Chemistry of CN Radicals on Ices: The formation of CH3CN and CH3NC and potential connection to acetamide

Context. Among the most significant chemical functional groups of interstellar molecules are the class of nitriles, which are proposed as key prebiotic molecules due to their chemical connection to the peptide bond after hydrolysis. CN radicals, the simplest representative of this group, have been shown to exhibit strong interactions with interstellar water ices, potentially impacting their reactivity with other radicals nearby. Aims. This study explores (a) whether CN and CH3 radicals can readily react to form methyl cyanide (CH3CN) and its isomer methyl isocyanide (CH3NC); and (b) the feasibility of the reaction (CN...H2O)hemi -> C(OH)=NH and its potential role in the formation of acetamide. Methods. Following a benchmark, density functional theory was employed to map the potential energy surfaces of these chemical processes, focusing on their reactivity on water and carbon monoxide ices. Results. The results show that CN reacts with CH3 radicals on water ices, forming CH3CN and CH3NC efficiently. However, these reactions are driven by diffusion of CH3 towards the reactive site and subsequently compete with back-diffusion of CH3 from that site. The formation of the radical intermediate C(OH)=NH on water ice requires quantum tunnelling and assuming that acetimidic acid forms via CH3 + C(OH)=NH -> CH3C(OH)=NH, it can also only isomerize into acetamide through a sizable barrier thanks to quantum tunnelling. Both quantum tunnelling-driven reactions are highly dependent on the local structure of the water ice. Finally, radical coupling reactions on carbon monoxide ices are found to be barrierless for all cases and again, both the cyanide and the isocyanide are formed. Conclusions. This work reinforces the conclusion that CN radicals on interstellar grain surfaces are highly reactive and unlikely to persist unaltered.

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arXiv2025

Toward Unraveling Cyanopolyyne Surface Chemistry: A Preview on Isolated Systems From HC_{3}N to Ethyl Cyanide and Propylamine

Cyanopolyynes, a family of nitrogen containing carbon chains, are common in the interstellar medium and possibly form the backbone of species relevant to prebiotic chemistry. Following their gas phase formation, they are expected to freeze out on ice grains in cold interstellar regions. In this work we present the hydrogenation reaction network of isolated HC_{3}N, the smallest cyanopolyyne, that consists over-a-barrier radical-neutral reactions and barrierless radical-radical reactions. We employ density functional theory, coupled cluster and multiconfigurational methods to obtain activation and reaction energies for the hydrogenation network of HC_{3}N. This work explores the reaction network of the isolated molecule and constitutes a preview on the reactions occurring on the ice grain surface. We find that the reactions where the hydrogen atom adds to the carbon chain at carbon atom opposite of the cyano-group give the lowest and most narrow barriers. Subsequent hydrogenation leads to the astrochemically relevant vinyl cyanide and ethyl cyanide. Alternatively, the cyano-group can hydrogenate via radical-radical reactions, leading to the fully saturated propylamine. These results can be extrapolated to give insight into the general reactivity of carbon chains on interstellar ices.

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arXiv2025

Hydrogenation of HOCO and formation of interstellar CO$_2$: A not so straightforward relation

Carbon dioxide (CO$_2$) is one of the most important interstellar molecules. While it is considered that it forms on the surface of interstellar dust grains, the exact contribution of different chemical mechanisms is still poorly constrained. Traditionally it is deemed that the CO + OH reaction occurring on top of ices is the main reaction path for its formation. Recent investigations showed that in reality the reaction presents a more complex mechanism, requiring an additional H-abstraction step. Building on our previous works, we carried out a detailed investigation of such H abstraction reactions with the hydrogen atom as a reactant for the abstraction reaction. We found an unconventional chemistry for this reaction, markedly depending on the isomeric form of the HOCO radical prior to reaction. The favored reactions are t-HOCO + H -> CO + H$_2$O, c-HOCO + H -> CO$_2$ + H$_2$ and t/c-HOCO + H -> c/t-HCOOH. We estimate bounds for the rate constants of the less favored reaction channels, t-HOCO + H -> CO$_2$ + H and c-HOCO + H -> CO + H$_2$O, to be approximately 10$^{4-6}$ s$^{-1}$. However, these estimates should be interpreted cautiously due to the significant role of quantum tunneling in these reactions and the complex electronic structure of the involved molecules, which complicates their study. Our findings underscore the need for detailed investigation into the chemistry of interstellar CO$_2$ and pave the way for a reevaluation of its primary formation mechanisms in the interstellar medium.

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arXiv2024

Formation of S-bearing complex organic molecules in interstellar clouds via ice reactions with C2H2, HS, and atomic H

The chemical network governing interstellar sulfur has been the topic of unrelenting discussion for the past decades due to the conspicuous discrepancy between its expected and observed abundances in different interstellar environments. More recently, the astronomical detections of CH3CH2SH and CH2CS highlighted the importance of interstellar formation routes for sulfur-bearing organic molecules with two carbon atoms. In this work, we perform a laboratory investigation of the solid-state chemistry resulting from the interaction between C2H2 molecules and SH radicals -- both thought to be present in interstellar icy mantles -- at 10 K. Reflection absorption infrared spectroscopy and quadrupole mass spectrometry combined with temperature-programmed desorption experiments are employed as analytical techniques. We confirm that SH radicals can kick-start a sulfur reaction network under interstellar cloud conditions and identify at least six sulfurated products: CH3CH2SH, CH2CHSH, HSCH2CH2SH, H2S2, and tentatively CH3CHS and CH2CS. Complementarily, we utilize computational calculations to pinpoint the reaction routes that play a role in the chemical network behind our experimental results. The main sulfur-bearing organic molecule formed under our experimental conditions is CH3CH2SH and its formation yield increases with the ratios of H to other reactants. It serves as a sink to the sulfur budget within the network, being formed at the expense of the other unsaturated products. The astrophysical implications of the chemical network proposed here are discussed.

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arXiv2023

Cracking the Puzzle of CO2 Formation on Interstellar Ices. Quantum Chemical and Kinetic Study of the CO + OH -> CO2 + H Reaction

CO2 is one of the dominant components of the interstellar ice. Recent observations show CO2 exists more abundantly in polar (H2O-dominated) ice than in apolar (H2O-poor) ice. CO2 ice formation is primarily attributed to the reaction between CO and OH, which has a barrier. Highly accurate quantum chemical calculations were employed to analyze the stationary points of the potential energy surfaces of the title reaction in the gas phase on a H2O and CO clusters. Microcanonical transition state theory was used as a diagnostic tool for the efficiency of the reaction under ISM conditions. We simulate the kinetics of ice chemistry, considering different scenarios involving non-thermal processes and energy dissipation. The CO + OH reaction proceeds through the remarkably stable intermediate HOCO radical. On the H2O cluster, the formation of this intermediate is efficient, but the subsequent reaction leading to CO2 formation is not. Conversely, HOCO formation on the CO cluster is inefficient without external energy input. Thus, CO2 ice cannot be formed by the title reaction alone either on the H2O cluster or CO cluster. In the polar ice, CO2 ice formation is possible via CO + OH -> HOCO, followed by HOCO + H ->CO2 + H2, as demonstrated by abundant experimental literature. In apolar ice, CO2 formation is less efficient because HOCO formation requires external energy. Our finding is consistent with the JWST observations. Further experimental work is encouraged using low-temperature OH radicals.

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arXiv2023

Streamers feeding the SVS13-A protobinary system: astrochemistry reveals accretion shocks?

We report ALMA high-angular resolution (~ 50 au) observations of the binary system SVS13-A. More specifically, we analyse deuterated water (HDO) and sulfur dioxide (SO2) emission. The molecular emission is associated with both the components of the binary system, VLA4A and VLA4B. The spatial distribution is compared to that of formamide (NH2CHO), previously analysed in the system. Deuterated water reveals an additional emitting component spatially coincident with the dust accretion streamer, at a distance larger than 120 au from the protostars, and at blue-shifted velocities (> 3 km/s from the systemic velocities). We investigate the origin of the molecular emission in the streamer, in light of thermal sublimation temperatures calculated using updated binding energies (BE) distributions. We propose that the observed emission is produced by an accretion shock at the interface between the accretion streamer and the disk of VLA4A. Thermal desorption is not completely excluded in case the source is actively experiencing an accretion burst.

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arXiv2022

The two hot corinos of the SVS13-A protostellar binary system: counterposed siblings

We present ALMA high-angular resolution ($\sim$ 50 au) observations of the Class I binary system SVS13-A. We report images of SVS13-A in numerous interstellar complex organic molecules: CH$_{\rm 3}$OH, $^{13}$CH$_{\rm 3}$OH, CH$_{\rm 3}$CHO, CH$_{\rm 3}$OCH$_{\rm 3}$, and NH$_{\rm 2}$CHO. Two hot corinos at different velocities are imaged in VLA4A (V$_{sys}$= +7.7 km s$^{-1}$) and VLA4B (V$_{sys}$= +8.5 km s$^{-1}$). From a non-LTE analysis of methanol lines we derive a gas density of 3 $\times$ 10$^8$ cm$^{-3}$, and gas temperatures of 140 K and 170 K for VLA4A and VLA4B, respectively. For the other species the column densities are derived from a LTE analysis. Formamide, which is the only N-bearing species detected in our observations, is more prominent around VLA4A, while dimethyl ether, methanol and acetaldehyde are associated with both VLA4A and VLA4B. We derive in the two hot corinos abundance ratios of $\sim$ 1 for CH$_{\rm 3}$OH, $^{13}$CH$_{\rm 3}$OH, and CH$_{\rm 3}$OCH$_{\rm 3}$, $\sim$ 2 for CH$_{\rm 3}$CHO, and $\sim$ 4 for NH$_{\rm 2}$CHO. The present dataset supports a chemical segregation between the different species inside the binary system. The emerging picture is that of an onion-like structure of the two SVS13-A hot corinos, caused by the different binding energies of the species, also supported by ad hoc quantum chemistry calculations. In addition, the comparison between molecular and dust maps suggests that the interstellar complex organic molecules emission originates from slow shocks produced by accretion streamers impacting the VLA4A and VLA4B disks and enriching the gas-phase component.

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arXiv2022

Quantum mechanical simulations of the radical-radical chemistry on icy surfaces

The formation of the interstellar complex organic molecules (iCOMs) is a hot topic in astrochemistry. One of the main paradigms trying to reproduce the observations postulates that iCOMs are formed on the ice mantles covering the interstellar dust grains as a result of radical--radical coupling reactions. We investigate iCOMs formation on the icy surfaces by means of computational quantum mechanical methods. In particular, we study the coupling and direct hydrogen abstraction reactions involving the CH$_3$ + X systems (X = NH$_2$, CH$_3$, HCO, CH$_3$O, CH$_2$OH) and HCO + Y (Y = HCO, CH$_3$O, CH$_2$OH), plus the CH$_2$OH + CH$_2$OH and CH$_3$O + CH$_3$O systems. We computed the activation energy barriers of these reactions as well as the binding energies of all the studied radicals, by means of density functional theory (DFT) calculations on two ice water models, made of 33 and 18 water molecules. Then, we estimated the efficiency of each reaction using the reaction activation, desorption and diffusion energies and derived kinetics with the Eyring equations. We find that radical--radical chemistry on surfaces is not as straightforward as usually assumed. In some cases, direct H abstraction reactions can compete with radical--radical couplings, while in others they may contain large activation energies. Specifically, we found that (i) ethane, methylamine and ethylene glycol are the only possible products of the relevant radical--radical reactions; (ii) glyoxal, methyl formate, glycolaldehyde, formamide, dimethyl ether and ethanol formation is likely in competition with the respective H-abstraction products, and (iii) acetaldehyde and dimethyl peroxide do not seem a likely grain surface products.

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arXiv2021

Theoretical computations on the efficiency of acetaldehyde formation on interstellar icy grains

Interstellar grains are known to be important actors in the formation of interstellar molecules such as H$_2$, water, ammonia, and methanol. It has been suggested that the so-called interstellar complex organic molecules (iCOMs) are also formed on the interstellar grain icy surfaces by the combination of radicals via reactions assumed to have an efficiency equal to unity. In this work, we aim to investigate the robustness or weakness of this assumption by considering the case of acetaldehyde (CH$_3$CHO) as a starting study case. In the literature, it has been postulated that acetaldehyde is formed on the icy surfaces via the combination of HCO and CH$_3$. Here we report new theoretical computations on the efficiency of its formation. To this end, we coupled quantum chemical calculations of the energetics and kinetics of the reaction CH$_3$ + HCO, which can lead to the formation of CH$_3$CHO or CO + CH$_4$. Specifically, we combined reaction kinetics computed with the Rice-Ramsperger-Kassel-Marcus (RRKM) theory (tunneling included) method with diffusion and desorption competitive channels. We provide the results of our computations in the format used by astrochemical models to facilitate their exploitation. Our new computations indicate that the efficiency of acetaldehyde formation on the icy surfaces is a complex function of the temperature and, more importantly, of the assumed diffusion over binding energy ratio $f$ of the CH$_3$ radical. If the ratio $f$ is $\geq$0.4, the efficiency is equal to unity in the range where the reaction can occur, namely between 12 and 30 K. However, if $f$ is smaller, the efficiency dramatically crashes: with $f$=0.3, it is at most 0.01. In addition, the formation of acetaldehyde is always in competition with that of CO + CH$_4$.

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arXiv2021

H2 formation on interstellar grains and the fate of reaction energy

Molecular hydrogen is the most abundant molecular species in the Universe. While no doubts exist that it is mainly formed on the interstellar dust grain surfaces, many details of this process remain poorly known. In this work, we focus on the fate of the energy released by the H$_2$ formation on the dust icy mantles, how it is partitioned between the substrate and the newly formed H$_2$, a process that has a profound impact on the interstellar medium. We carried out state-of-art \textit{ab-initio} molecular dynamics simulations of H$_2$ formation on periodic crystalline and amorphous ice surface models. Our calculations show that up to two thirds of the energy liberated in the reaction ($\sim$300 kJ/mol $\sim$3.1 eV) is absorbed by the ice in less than 1 ps. The remaining energy ($\sim$140 kJ/mol $\sim$1.5 eV) is kept by the newly born H$_2$. Since it is ten times larger than the H$_2$ binding energy on the ice, the new H$_2$ molecule will eventually be released into the gas-phase. The ice water molecules within $\sim$4 Å~from the reaction site acquire enough energy, between 3 and 14 kJ/mol (360--1560 K), to potentially liberate other frozen H$_2$ and, perhaps, frozen CO molecules. If confirmed, the latter process would solve the long standing conundrum of the presence of gaseous CO in molecular clouds. Finally, the vibrational state of the newly formed H$_2$ drops from highly excited states ($ν= 6$) to low ($ν\leq 2$) vibrational levels in a timescale of the order of ps.

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arXiv2020

Chemical desorption versus energy dissipation: insights from ab-initio molecular dynamics of HCO formation

Molecular clouds are the cold regions of the Milky Way where stars form. They are enriched by rather complex molecules. Many of these molecules are believed to be synthesized on the icy surfaces of the interstellar submicron-sized dust grains that permeate the Galaxy. At 10 K thermal desorption is ineffcient and, therefore, why these molecules are found in the cold gas has tantalized astronomers for years. The assumption of the current models, called chemical desorption, is that the molecule formation energy released by the chemical reaction at the grain surface is partially absorbed by the grain and the remaining one causes the ejection of the newly formed molecule into the gas. Here we report an accurate ab-initio molecular dynamics simulations aimed to study the fate of the energy released by the first reaction of the H addition chain on CO, CO + H $\rightarrow$ HCO, occurring on a crystalline ice surface model. We show that about 90% of the HCO formation energy is injected towards the ice in the first picosecond, leaving HCO with an energy content (10-15 kJ mol$^{-1}$) more than a factor two lower than its adsorption energy (30 kJ mol$^{-1}$). As a result, in agreement with laboratory experiments, we conclude that chemical desorption is ineffcient for this specific system, namely H + CO on crystalline ice. We suspect this behavior to be quite general when dealing with hydrogen bonds, which are responsible of both the cohesive energy of the ice mantle and the interaction with adsorbates, as the HCO radical, even though ad hoc simulations are needed to draw specific conclusions on other systems.

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arXiv2019

Reactivity of HCO with CH3 and NH2 on Water Ice Surfaces. A Comprehensive Accurate Quantum Chemistry Study

Interstellar complex organic molecules (iCOMs) can be loosely defined as chemical compounds with at least six atoms in which at least one is carbon. The observations of iCOMs in star-forming regions have shown that they contain an important fraction of carbon in a molecular form, which can be used to synthesize more complex, even biotic molecules. Hence, iCOMs are major actors in the increasing molecular complexity in space and they might have played a role in the origin of terrestrial life. Understand-ing how iCOMs are formed is relevant for predicting the ultimate organic chemistry reached in the interstellar medium. One possibility is that they are synthesized on the interstellar grain icy surfaces, via recombination of previously formed radicals. The present work focuses on the reactivity of HCO with CH3/NH2 on the grain icy sur-faces, investigated by means of quantum chemical simulations. The goal is to carry outa systematic study using different computational approaches and models for the icy surfaces. Specifically, DFT computations have been bench-marked with CASPT2 and CCSD(T) methods, and the ice mantles have been mimicked with cluster models of 1, 2, 18 and 33 H2O molecules, in which different reaction sites have been considered. Our results indicate that the HCO + CH3/NH2 reactions, if they actually occur, have two major competitive channels: the formation of iCOMs CH3CHO/NH2CHO, or the formation of CO + CH4/NH3. These two channels are either barrierless or presentrelatively low ($\leq$ 10 kJ/mol equal to about 1200 K) energy barriers. Finally, we briefly discuss the astrophysical implications of these findings.

astro-ph.SR↗

arXiv2018

Can Formamide Be Formed on Interstellar Ice? An Atomistic Perspective

Interstellar formamide (NH2CHO) has recently attracted significant attention due to its potential role as a molecular building block in the formation of precursor biomolecules relevant for the origin of life. Its formation, whether on the surfaces of the interstellar grains or in the gas phase, is currently debated. The present article presents new theoretical quantum chemical computations on possible NH2CHO formation routes in water-rich amorphous ices, simulated by a 33-H2O-molecule cluster. We have considered three possible routes. The first one refers to a scenario used in several current astrochemical models, that is, the radical-radical association reaction between NH2 and HCO. Our calculations show that formamide can indeed be formed, but in competition with formation of NH3 and CO through a direct H transfer process. The final outcome of the NH2 + HCO reactivity depends on the relative orientation of the two radicals on the ice surface. We then analyzed two other possibilities, suggested here for the first time: reaction of either HCN or CN with water molecules of the ice mantle. The reaction with HCN has been found to be characterized by large energy barriers and, therefore, cannot occur under the interstellar ice conditions. On the contrary, the reaction with the CN radical can occur, possibly leading through multiple steps to the formation of NH2CHO. For this reaction, water molecules of the ice act as catalytic active sites since they help the H transfers involved in the process, thus reducing the energy barriers (compared to the gas-phase analogous reaction). Additionally, we apply a statistical model to estimate the reaction rate coefficient when considering the cluster of 33-H2O-molecules as an isolated moiety with respect to the surrounding environment, i.e., the rest of the ice.

astro-ph.EP↗

arXiv2016

The (impossible?) formation of acetaldehyde on the grain surfaces: insights from quantum chemical calculations

Complex Organic Molecules (COMs) have been detected in the interstellar medium (ISM). However, it is not clear whether their synthesis occurs on the icy surfaces of interstellar grains or via a series of gas-phase reactions. As a test case of the COMs synthesis in the ISM, we present new quantum chemical calculations on the formation of acetaldehyde (CH3CHO) from the coupling of the HCO and CH3 radicals, both in gas phase and on water ice surfaces. The binding energies of HCO and CH3 on the amorphous water ice were also computed (2333 and 734 K, respectively). Results indicate that, in gas phase, the products could be either CH3CHO, CH4 + CO, or CH3OCH, depending on the relative orientation of the two radicals. However, on the amorphous water ice, only the CH4 + CO product is possible due to the geometrical constraints imposed by the water ice surface. Therefore, acetaldehyde cannot be synthesized by the CH3 + HCO coupling on the icy grains. We discuss the implications of these results and other cases, such as ethylene glycol and dimethyl ether, in which similar situations can occur, suggesting that formation of these molecules on the grain surfaces might be unlikely.

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